Re(I) tricarbonyl bipyridine and terpyridine complexes catalyse stereospecific cyclopropanation of alkenes; high selectivity of cyclopropanevs coupling and an ee of 73% and 62% for cis- and trans-cyclopropanes of styrene respectively were achieved with the [Re(L)(CO)3(MeCN)]OTf complex (L = chiral C2-symmetric terpyridineligand).